Applied Surface Science 255 (2009) 70407046

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Study on the hydrophobic surfaces prepared by two-step solgel process

Shi-Ing Huang a,b, Yi-Ju Shen c, Hui Chen a,c,*
a

Department of Chemical and Materials Engineering, National Central University, Taoyuan County 32001, Taiwan, ROC Material and Chemical Research Laboratories, Industrial Technology Research Institute, Chutung, Hsinchu 31015, Taiwan, ROC c Graduate Institute of Materials Science and Engineering, National Central University, Taoyuan County 32001, Taiwan, ROC
b

A R T I C L E I N F O

A B S T R A C T

Article history: Received 17 October 2008 Received in revised form 12 March 2009 Accepted 13 March 2009 Available online 24 March 2009 Keywords: Hydrophobic Solgel TEOS Viscosity Contact angle

In this study, the two-step solgel process was used to prepare hydrophobic coating lms on the glass substrates. The rst step was to add hydrogen chloride into TEOS (tetraethoxysilane) solution, and then the second step was to add ammonia into the above reacted solution. We adopted different amount of hydrogen chloride and ammonia to control the solgel reaction and observed the change of the viscosity, gelatin period of the solution and contact angles of the coating lms. By this method, we created a surface with roughness and then the hydroxyl groups were terminated by adding trimethylchlorosilane (TMCS) to produce a hydrophobic coating layer. The amount of the acid, base and water added in the solution inuenced the reaction rate and resulted in the aggregation and condensation of the particles to form rough surfaces. Consequently, the rough surfaces made by aggregation and condensation of the large particles, which were modied by TMCS resulted in higher contact angles (>1408). In this study, a surface with contact angle 1508 was obtained. 2009 Elsevier B.V. All rights reserved.

1. Introduction Hydrophobic surface is an active area of research in recent years. Hydrophobic lms on glass substrates with water repellency have many applications such as windows of buildings, windshilds of automobiles, bathroom mirrors [12], and so on. The dust on the hydrophobic lms can be taken away by rain drops. Hydrophobic coating lms made with different methods have been studied. For example, hydrophobic coating lms on glass substrates can be prepared by coating uoroalkyltrimethoxysilane (FAS) [13] to control the hydrophobic groups on the surface, or by solgel processes to make a lm with rough surface on a glass substrate, which is followed by end-capping process to terminate hydroxyl groups [46]. Besides, hydrophobic lms can also be made by using different co-precursors via solgel processes [7 10]. Solgel processes have two mechanisms including hydrolysis and condensation. Usually, the solgel processes were catalyzed by acid, base or both of them (two-step solgel process) [714]. H.M. Shang et al. [9] proposed the models to illustrate the possible microstructures of the lms made by the sols coated on glass substrates. If the acidic sol was coated on a glass, linear silica-based

oligomer or polymer chains pack to form a relatively dense and smooth lm. If the basic solution was coated on a glass, a lm with rough surface synthesized by the stack of the round particles was obtained. In this study, the two-step solgel process was used to prepare hydrophobic coating lms on the glass substrates. The rst step was to add hydrogen chloride into TEOS solution, and then the second step was to add ammonia into the above reacted solution. We adopted different amount of hydrogen chloride and ammonia to control the solgel reaction and observed the change of the viscosity, gel time of the sol and contact angles of the coating lms. By this method, we created a surface with roughness and then the hydroxyl groups were terminated by adding trimethylchlorosilane (TMCS) to produce a hydrophobic coating layer, even a superhydrophobic coating layer. (If the contact angle of water droplet on a solid surface is greater than 1508, then the surface is called superhydrophobic [11].) 2. Experiment 2.1. Materials Tetraethoxysilane (TEOS, reagent grade), and trimethylchlorosilane (TMCS, reagent grade) were all purchased from Shin-Etsu Chemical Co. Ltd., Japan. Other reagents were hydrochloric acid (HCl) (Merck, reagent grade), ammonium hydroxide (NH4OH) (Merck, reagent grade), ethanol (EtOH) (ECHO, reagent grade), and n-hexane (NASA, certied grade).

* Corresponding author at: No. 300, Jhongda Rd., Jhongli City, Taoyuan County 32001, Taiwan, ROC. Tel.: +886 3 4227151x34216; fax: +886 3 425 2296. E-mail address: huichen@cc.ncu.edu.tw (H. Chen). 0169-4332/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.apsusc.2009.03.037

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2.2. Sample preparation During the two-step solgel process, the amount of water and HCl added in the rst step was very important, because the hydrolysis of the solutions was inuenced by those. In this study, Let R Ra Rb (1)

where R was the total molar ratio of water/TEOS in the reaction, and Ra and Rb was the molar ratio of water/TEOS in the rst and the second step of the reaction, respectively. Preparation of hydrophobic surfaces by the two-step solgel process was described as follows. In the rst step, TEOS was dissolved in ethanol. And pure water (Ra) and HCl (1N) were added in the solution, and let the solution reacted at 60 8C for 1.5 h. Then, the solution was cooled down to room temperature. In the second step, pure water (Rb) and NH4OH (28 wt.%) were added in the solution, and the solution was mixed well, and the viscosity of the solution was measured. The solution was drawn out to be spin coated on a glass plate every 15 min. The speed of the spin coater was controlled at 500 600 rpm for 10 s and then it was controlled at 11001200 rpm for another 10 s. (Two-step spin coating process made a at lm, because the solution was shear thinning [15].) After the spin coating process, the sample was baked at 50 8C for 1 h. When the sample was cooled down to room temperature, it was immersed in TMCS solution (10 wt.% in hexane) for two days to replace the hydroxyl groups [16]. The TMCS was excess for replacing the hydroxyl groups. Then, the samples were washed with hexane, and baked at 80 8C for 1 h to remove the solvent. 2.3. Measurements 2.3.1. Viscosity of the solution The viscosity of the solution in the second step was measured by Vibro viscometer SV-10. When the base catalyst was added, the viscometer started to measure the viscosity value at once. 2.3.2. Contact angle To quantify the degree of hydrophobicity, the contact angle (u) of water droplet placed on the hydrophobic surface was measured by Kyowa interface sciences CA-D and calculated using the formula Tan (u/2) = 2 h/W, where W was the base contact length and h was the height of the droplet. These values were measured by using a microscope. 2.3.3. FTIR The surface modication was conrmed using FTIR spectroscopy (Perkin Elmer instruments, spectrum one). 3. Results and discussion 3.1. The change of the viscosity of the solution In general, the hydrolysis of TEOS was preferred under acidic condition. On the other hand, the condensation was facilitated under basic condition. Two-step solgel process makes it possible to remove slow hydrolysis step under basic conditions and slow condensation step under acidic conditions and to individually tune each step to design solgel derived materials microscopically or macroscopically unique properties [17,18]. In the rst step, only some water and acid were mixed with TEOS and ethanol. Therefore, the hydrolysis was not complete, and the degree of polymerization was little, and even only partial hydrolyzed monomer was in the system. As the base and more

Fig. 1. Effect of the reaction time on the inverse of the viscosity. (The molar ratio of TEOS:Ra:R:HCl:NH4OH = 1:0.5:2.3:3.36 104:3.78 103.)

water were added in the second step, the condensation was promoted. It resulted in a decrease of gelatin period. After the base was added in the solution, the viscosity of the solution was almost the same for a certain time corresponding to the formation of small clusters of branched silica polymers [19]. Suddenly, the viscosity of the solution increased rapidly as the clusters aggregated, and the size of the clusters grew up quickly. It was known that the viscosity of the solution was innite approach at the gel point (tg). Therefore, the inverse of the viscosity was zero at tg. A plot of the inverse of the viscosity versus reaction time, which the tg was estimated by extrapolating the inverse of the viscosity to time axis, was shown in Fig. 1. In this study, we tted the data of the inverse of the viscosity at the early stage of the second step as a straight line because the viscosity did not change a lot during the period. Then, we tted the data of the inverse of viscosity at the nal stage of the second step as another straight line. We assumed the intersection point of these two lines as the onset point (ts) shown in Fig. 1. It was dened that viscosity started to increase rapidly at ts [19]. ts can be considered as a macroscopic initial gelatin period, although microscopic initial gelatin would occur earlier than this point. The viscosity barely changes, or slowly increases during the early stage of measurement [20]. But as the reaction time reached ts, the reaction rate increased. After that point, the viscosity became higher and higher, and it was not easy to coat the solution on a glass plate. On the contrary, it was easy to coat the solution on a glass plate due to lower viscosity of the solution and a smooth surface with 1101208 water contact angle was expected due to smaller size of the particles before ts. As mentioned above, the rough surface of the lms could be obtained while the solution was prepared at ts or near ts. So, it is important to nd out ts and tg by a measurement of viscosity. 3.2. The effect of Ra In the experiments, the molar ratio of TEOS, water, HCl and NH4OH was kept constant (TEOS:Rb:HCl:NH4OH = 1:3:3.36 104:3.78 103). Ra was varied in the reaction. When the reaction time of the second step was at 15 min, the solutions were coated on glass plates and the contact angle of the lms was dened as CA15min. The effect of Ra on ts and tg of the solutions and CA15min of the lms was shown in Fig. 2. It showed that ts and tg decreased with increasing Ra. It was considered that more water being added in the rst step made monomers had more hydroxyl groups (functionality). And these functionality in the solutions made the condensation rate increased in the second step [21]. Consequently, ts and tg decreased.

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Fig. 2. Effect of Ra on ts and tg of the solution prepared by the molar ratio of TEOS:R:HCl:NH4OH = 1:3.5:3.36 104:3.78 103, and CA15min of the lms prepared by the above solutions.

Fig. 3. FTIR spectrum of the sample. The recipe of the sample was TEOS:Ra:R:HCl:NH4OH = 1:0.5:3.5:3.36 104:3.78 103. The reaction time of the sample was 15 min after ammonia was added.

Theoretically, when R = 2, the hydrolysis of TEOS is complete. Therefore, as Ra = 1.5, the degree of the hydrolysis was high, which made the condensation fast in the second step. It made tg and ts become 10, and 6 min, respectively. So, more Ra made the condensation faster under basic condition. According to the CA15min shown in Fig. 2, CA15min decreased with increasing Ra. When Ra was 0.4, 0.5 and 0.75, the monomers in the solutions with functionality would form larger clusters. It made the rough surfaces and result in high contact angles. However, more Ra would result in the linear growth of the molecules in the solutions under acidic solution. And the condensation of the linear molecules in the second step could make smooth surface. Therefore, the increment of Ra made the roughness of the surfaces of the lms decreased and resulted in lower contact angles. Fig. 3 is the FTIR spectrum the sample. (The recipe of the sample was TEOS:Ra:R:HCl:NH4OH = 1:0.5:3.5:3.36 104:3.78 103. The reaction time of the sample was 15 min after ammonia was added.) It showed that there were absorption bands at 2900 cm1 and 1270 cm1corresponding to CH and SiC bonds. It conrmed that the surface was modied by TMCS. There is also an absorption band at 3500 cm1 corresponding to OH. But the CA15min is about 1458. It indicated that the unmodied hydroxyl groups might be in the structure but did not inuence the contact angle. Fig. 4 showed the SEM images of the lms of CA15min shown in Fig. 2. The SEM images showed that the surfaces of the lms became smoother when Ra was greater than 0.75. It agreed with the result of CA15min. Fig. 5 is the effect of reaction time on contact angles of the lms, which were made with different Ra. When Ra 0.75, the data of

CA15min ! 1408 and the curves of contact angles of the lms were almost higher than 1408. But as Ra = 1.25, CA15min was only about 1208. As Ra = 1.25, the reaction rate was fast, and tg < 30. Therefore, when reaction time was 30 min, the sample could not be coated on a glass plate. According to Fig. 5, when the reaction time was larger than 15 min, the curves of the contact angles did not change a lot with reaction time. When the CA15min ! 1408, the curves of the contact angles might be larger than 1408. Thus, CA15min might be an index to tell which recipe could make a lm with contact angle ! 1408. In this study, when 0.4 Ra 0.75, there were lms with contact angle more than 1408 obtained and ts was at the range of 1648 min. It not only made the lms with high contact angle but also provided enough time for coating process. 3.3. The effect of the amount of HCl added in the rst step of solgel process Then, the effect of the amount of HCl added in the rst step of solgel process is discussed as follows. In the experiments, TEOS:Ra:R:NH4OH = 1:0.5:3.5:3.78 103 and the molar ratio of HCl/TEOS was varied from 0.84 104 to 5.04 104. The effect of the molar ratio of HCl/TEOS on ts and tg of the solutions and CA15min of the lms were shown in Fig. 6. When the molar ratio of HCl/TEOS increased from 0.84 104 to 3.36 104, tg decreased from 114 to 61 min and ts decreased from 74 to 35 min. In the rst step of the solgel process, Ra was 0.5, and more HCl being added in the solutions made the rate of hydrolysis faster. And more silanols in the system were obtained in the constant reaction time. After NH4OH was added in the second step, more silanols made the condensation rate increased. Therefore, ts and tg decreased. However, when the molar ratio of HCl/TEOS was greater than

Fig. 4. The SEM images of the lms of the CA15min shown in Fig. 2, and Ra values were (A) 0.4, (B) 0.5, (C) 0.75, and (D) 1.25, respectively. (The scale bar is 2 mm.)

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Fig. 5. Effect of the reaction time on contact angles of the lms, which were made with different Ra.

Fig. 7. Effect of reaction time on contact angles of the lms.

The SEM images of the lms prepared by different molar ratio of HCl/TEOS were shown in Fig. 8. There were large particles formed in the solution of higher concentration of HCl, and the solution could make a lm with rougher surface resulting in higher contact angle (Fig. 8C). More silanols in the solutions would produce more particles. Then, the particles might reorganize into fewer larger particles corresponding to reduction in the surface energy [22] and resulted in rougher surfaces. However, when concentration of HCl is higher, the large particles condensing further might result in the decrement of roughness (Fig. 8D). Since the molar ratio of HCl/ TEOS ! 3.36 104, the lms had high contact angle and proper ts for the coating process. In the following experiments, the molar ratio of HCl/TEOS was kept at 3.36 104. 3.4. The effect of the amount of NH4OH in the second step of the sol gel process In the second step of the solgel process, NH4OH was added into the solutions to catalyze the reaction. In these experiments, TEOS:Ra:R:HCl was xed to 1:0.5:3.5:3.36 104, and NH4OH/ HCl molar ratio was varied from 5.6 to 26.8. The pH values of the solutions were in the range of 8.08.6. The effect of NH4OH/HCl molar ratio on ts and tg of the solutions and CA15min of the lms prepared by the above solutions were shown in Fig. 9. When NH4OH/ HCl molar ratio increased, tg and ts decreased. Hydrolysis and condensation occurred as NH4OH was added in the second step. When the amount of NH4OH increased, it would accelerate the reaction rate. As a result, tg and ts decreased. When NH4OH/HCl molar ratio was larger than 19.1, tg and ts did not change a lot due to the depolymerization and polymerization. According to the CA15min shown in Fig. 9, the data of CA15min were almost higher than 1408 when NH4OH/HCl molar ratio was larger than 5.6. The SEM images of the lms of the CA15min prepared by different NH4OH/HCl molar ratio were shown in Fig. 10. When NH4OH/HCl molar ratio = 5.6, the condensation rate was slow and very small particles were formed. Therefore, when the small particles aggregated, there was a smooth surface obtained (Fig. 10A) and resulted in lower contact angle of the surface. When NH4OH/HCl molar ratio was larger than 5.6, the condensation rate increased with the increment of NH4OH/HCl molar ratio and larger particles were formed. Consequently, the rough surfaces (Fig. 10BD) made by aggregation of the large particles, which resulted in higher contact angles (>1408). The effect of reaction time on contact angle of the lms was shown in Fig. 11. When NH4OH/HCl molar ratio was 5.6, the contact angle decreased at the early stage of the reaction. When reaction time was larger than 75 min, the contact angle started to increased. The contact angle changed few after 120 min. The effect of reaction time on contact angle of the lms can be understood by

Fig. 6. Effect of the molar ratio of HCl/TEOS on ts and tg of the solution prepared by the molar ratio of TEOS:Ra:R:NH4OH = 1:0.5:3.5:3.78 103, and contact angles of the lms prepared by the above solution.

3.36 104, tg increased slightly from 61 to 65 min due to water being consumed in the constant reaction time of the rst step, which led to dimersation resulting in a decrease of the monomeric silanol concentration. In the second step, nucleation and growth is the dominant mechanism under basic conditions and silanols (deprotonated) are the preferred growth sites [22]. Consequently, there were fewer silanols in the solution due to dimersation, which resulted in a decrease of reaction rate. And tg increased a little. According to the CA15min shown in Fig. 6, when the molar ratio of HCl/TEOS was greater than 3.36 104, the CA15min was greater than 1408. When the molar ratio of HCl/TEOS was lower than 1.68 104, the CA15min was less than 1208. Thus, the molar ratio of HCl/TEOS being greater than 3.36 104 made lms with higher contact angles. Fig. 7 is the effect of reaction time on contact angles of the lms. When the molar ratio of HCl/TEOS 1.68 104, the contact angles of the lms increased with reaction time at the early stage, and then the contact angles were kept between 1328 and 1388. When more acid was added in the solution, the reaction rate was faster, and resulted in the aggregation and condensation of the particles to form rough surfaces. Therefore, the contact angle increased faster. When the molar ratio of HCl/TEOS ! 3.36 104, the contact angles were all greater than 1428, and the greatest one could be greater than 1508. Consequently, a lm of high contact angle had a rougher surface due to the faster reaction rate at higher HCl concentration in the solutions.

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Fig. 8. The SEM images of the lms prepared by the molar ratio of TEOS:Ra:R:NH4OH = 1:0.5:3.5:3.78 103 with different molar ratio of HCl/TEOS (A) 8.4 105, (B) 1.68 104 (C) 3.36 104 and (D) 5.04 104. The contact angle of the lms is the greatest in each recipe. The contact angle is (A) 1388, (B) 139.28 and (C) 1518 and (D) 145.88, respectively. (The scale bar is 2 mm.)

Fig. 9. Effect of NH4OH/HCl molar ratio on ts and tg and contact angles (the molar ratio of TEOS:Ra:R:HCl = 1:0.5:3.5:3.36 104).

When NH4OH/HCl molar ratio was lager than 5.6, the contact angle was high at the early stage of the reaction. With the increasing reaction time, the contact angle changed few, because there were large particles formed at the early stage of the reaction, which resulted in little difference of the morphology of the surfaces. When NH4OH/HCl molar ratio was 7.4, the contact angle decreased when the reaction time was larger than 60 min. It was found by the SEM images (Fig. 12EH) that the large particles would aggregate and condense further because there was still about 50 min to reach the tg. It made the roughness of the lms decreased and resulted in the contact angle decreasing more than 108. When NH4OH/HCl molar ratio was 11.3, it was found via observing the SEM images (Fig. 12IK) of the lms prepared at different reaction time that there were large particles formed to make rough surface, which resulted in high contact angle. When the reaction time was larger than 30 min, the contact angle decreased. This result was also caused by the further aggregation and condensation of the particles, because the reaction time did not reach tg. In this part of the study, it was found that there were lms with high contact angle formed, when NH4OH/HCl molar ratio was greater than 5.6. 3.5. The effect of R values Water was not only a reactant but also a product in the solgel process, and more water added in the solutions could accelerate the reaction. The ratio, TEOS:Ra:HCl was xed to 1:0.5:3.36 104, and R value was varied. The effect of R on the ts and tg of the solutions, and the CA15min of the lms prepared by the above solutions were shown in Fig. 13. It was found that tg and ts decreased as R value increased. However, when R was larger than 3.5, tg and ts did not change a lot. In the rst step of the reaction, the water ratio Ra was only 0.5. It was expected that there was a little

the SEM images of the lms prepared at different reaction time shown in Fig. 12. At the early stage of the reaction, there were very small particles formed. When the small particles aggregated, there was a smooth surface obtained (Fig. 12A). When reaction time was at 75 min, the small particles aggregated and condensed to form a smoother surface (Fig. 12B). Then, with the increasing reaction time, more particles were formed and the surface of the lm was rough (Fig. 12C), which increased the contact angle. When reaction time was larger than 120 min, the particles aggregated and condensed further to form a rougher surface (Fig. 12D). Then, the lms had higher contact angle and the contact angle changed few.

Fig. 10. The SEM images of the lms of the CA15min as shown in Fig. 8, and NH4OH/HCl molar ratio was (A) 5.6, (B) 7.4, (C) 11.3, and (D) 19.1, respectively. (The scale bar is 2 mm.)

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Fig. 11. Effect of reaction time on contact angle of the lms.

amount of monomer to be hydrolyzed, and the hydrolyzed monomers had less functionality. But with increasing R, the hydrolysis and functionality of the monomer increased and the condensation rate was also accelerated.

According to the CA15min shown in Fig. 13, when R increased from 2.3 to 2.9, the CA15min of the surfaces of the lms was lower than 1408 due to less silanols in the solutions to form small particles. When R increased from 3.5 to 4.1, there was enough amount of water to hydrolyze the monomers. Thus, there were large particles being formed in the solutions. The lms made by such solutions had rough surfaces, which had high contact angle. The effect of reaction time on contact angles of the lms was shown in Fig. 14. When R was 2.3, there was not enough water for monomers to be hydrolyzed. Therefore, the reaction rate was slow. Thus, the contact angle decreased from the early stage of the reaction. When the reaction time was larger than 50 min, the contact angle started to increase. The contact angle changed few after 75 min. When reaction time was at 30 min, there were small particles being formed. And the particles aggregated. Thus, there was a smooth surface obtained (Fig. 15A). When reaction time was at 45 min, the small particles aggregated and condensed to form a smoother surface (Fig. 15B). Then, with the increasing reaction time, more particles were formed and made the surface of the lm rough (Fig. 15C), which increased the contact angle. When reaction time was larger than 75 min, the particles aggregated and condensed further to form a rougher surface (Fig. 15D), which had higher contact angle and the contact angles changed few.

Fig. 12. The SEM images of the lms prepared by different NH4OH/HCl molar ratio at different reaction time. When NH4OH/HCl molar ratio was 5.6, the reaction time of image A, B, C and D was 15, 75, 105 and 195 min, respectively. When NH4OH/HCl molar ratio was 7.4, the reaction time of image E, F, G and H was 30, 45, 60 and 75 min, respectively. When NH4OH/HCl molar ratio was 11.3, the reaction time of image I, J, and K was 15, 30, 45 min, respectively. (The scale bar is 2 mm.)

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Fig. 13. Effect of R values on ts and tg of the solutions and contact angles of the lms. The solutions and lms were prepared by the molar ratio of TEOS:Ra:HCl:NH4OH = 1:0.5:3.36 104:3.78 103.

Fig. 14. Effect of reaction time on contact angles of the lms.

Fig. 15. The SEM images of the lms prepared at different reaction time when R was 2.3. The reaction time was (A) 30, (B) 45, (C) 75 and (D) 90 min, respectively. (The scale bar is 2 mm.)

When R ! 2.9, there was more water to react with monomers and more silanols were obtained. It made the reaction rate faster, and there were large particles produced. Via the aggregation and condensation, the contact angle of the lms increased with the increment of the reaction time. After that, the contact angle of the lms would not change a lot. When R was larger than 2.9, the contact angle of the lms were almost higher than 1408. If a lm of high contact angle is preferred, the R must be larger than 2.9. 4. Conclusion In the two-step solgel process, ts, and tg decreased as Ra increased, because more water added in the rst step of the reaction promoted the reaction of hydrolysis and produced more silanols. When more acid was added in the solution, the reaction rate was faster, and resulted in the aggregation and condensation of the particles to form rough surfaces. Therefore, the contact angle increased faster. When the amount of NH4OH increased, the reaction rate was accelerated, and resulted in a decrease of tg and ts. In this study, when NH4OH/HCl molar ratio was larger than 5.6, the condensation rate increased with the increment of NH4OH/HCl molar ratio and larger particles were formed. Consequently, the rough surfaces made by aggregation of the large particles, which resulted in higher contact angles (>1408). When R was larger than 2.9, the contact angle of the lms were almost higher than 1408. References
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